US6987071B1 - Solvent vapor infiltration of organic materials into nanostructures - Google Patents

Solvent vapor infiltration of organic materials into nanostructures Download PDF

Info

Publication number
US6987071B1
US6987071B1 US10/719,041 US71904103A US6987071B1 US 6987071 B1 US6987071 B1 US 6987071B1 US 71904103 A US71904103 A US 71904103A US 6987071 B1 US6987071 B1 US 6987071B1
Authority
US
United States
Prior art keywords
poly
derivatives
organic material
nanostructures
polyfluorene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related, expires
Application number
US10/719,041
Inventor
Brent J. Bollman
Klaus Petritsch
Matthew R. Robinson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aeris Capital Sustainable IP Ltd
Original Assignee
Nanosolar Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanosolar Inc filed Critical Nanosolar Inc
Priority to US10/719,041 priority Critical patent/US6987071B1/en
Assigned to NANOSOLAR INC. reassignment NANOSOLAR INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BOLLMAN, BRENT J., PETRITSCH, KLAUS, ROBINSON, MATTHEW R.
Application granted granted Critical
Publication of US6987071B1 publication Critical patent/US6987071B1/en
Assigned to AERIS CAPITAL SUSTAINABLE IMPACT PRIVATE INVESTMENT FUND CAYMAN L.P. reassignment AERIS CAPITAL SUSTAINABLE IMPACT PRIVATE INVESTMENT FUND CAYMAN L.P. SECURITY AGREE,EMT Assignors: NANOSOLAR, INC.
Assigned to AERIS CAPITAL SUSTAINABLE IP LTD. reassignment AERIS CAPITAL SUSTAINABLE IP LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NANOSOLAR, INC.
Adjusted expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H10K71/441—Thermal treatment, e.g. annealing in the presence of a solvent vapour in the presence of solvent vapors, e.g. solvent vapour annealing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • H10K30/352—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles the inorganic nanostructures being nanotubes or nanowires, e.g. CdTe nanotubes in P3HT polymer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/114—Poly-phenylenevinylene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/221—Carbon nanotubes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
    • Y10S977/753—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc. with polymeric or organic binder
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/84—Manufacture, treatment, or detection of nanostructure
    • Y10S977/895—Manufacture, treatment, or detection of nanostructure having step or means utilizing chemical property

Definitions

  • the present invention relates to processing of organic materials and more particularly to filling spaces in nanostructures with organic materials.
  • FIGS. 1A–1C are a sequence of cross-sectional schematic diagrams illustrating a method for solvent vapor infiltration of a polymer into a nanostructure according to an embodiment of the present invention.
  • FIGS. 1D–1E are a sequence of cross-sectional schematic diagrams illustrating fabrication of a device.
  • FIGS. 2A–2B are a sequence of schematic diagrams illustrating solvent vapor infiltration of a polymer into nanotubes according to an alternative embodiment of the present invention.
  • empty spaces in a nanostructure can be filled with a polymer or other organic material (such as a small molecule, e.g., fullerene, pigment, or dye) at room temperature by lowering the glass transition temperature T g by exposing the polymer to solvent vapor while on or mixed with the nanostructured material.
  • a polymer or other organic material such as a small molecule, e.g., fullerene, pigment, or dye
  • T g glass transition temperature
  • an organic material 110 is disposed on a nanostructured material 102 .
  • the nanostructured material may be formed or otherwise disposed on an electrode 104 , e.g., a metal foil.
  • the electrode 104 may be disposed on a substrate 106 such as a glass or polymer.
  • the organic material 110 is a conducting or semiconducting polymer.
  • polymers include poly(phenylene) and derivatives thereof, poly(phenylene vinylene) and derivatives thereof (e.g., poly(2-methoxy-5-(2-ethyl-hexyloxy)-1,4-phenylene vinylene (MEH—PPV), poly(para-phenylene vinylene), (PPV)), PPV copolymers poly(thiophene) and derivatives thereof (e.g., poly(3-octylthiophene-2,5,-diyl), regioregular, poly(3-octylthiophene-2,5,-diyl), regiorandom, poly(3-hexylthiophene) (P3HT), poly(3-hexylthiophene-2,5-diyl), regioregular, poly(3-hexylthiophene-2,
  • P3HT poly(3
  • the organic material 110 can be a fullerene, dye, pigment or other organic molecule such as pentacene or pentacene precursors.
  • the organic material 110 may be disposed on the nanostructured material 102 by any suitable technique, e.g., spin coating, web coating, doctor blade coating, spray coating, inkjet printing, organic vapor jet printing and the like.
  • the nanostructured material has numerous spaces 108 that are several nanometers across, e.g., between about 50 nm and about 1000 nm across.
  • the nanostructures can be in the form of tubes in a nanotubular template, e.g., 1 nm to 1000 nm in diameter with a tube density between about 10 12 tubes/m 2 and about 10 16 tubes/m 2 .
  • the spaces 108 can be nanopores, cavities, or interstitial spaces between pores, tubes or rods.
  • the nanostructured material 102 may be fabricated by anodization techniques or surfactant temptation techniques. Examples of anodization techniques are described e.g., in commonly assigned co-pending U.S. patent application Ser. No.
  • the organic material 110 is exposed to a solvent vapor 112 .
  • a solvent vapor 112 For example, when the organic material 110 is a polymer, exposure to the solvent vapor 112 mobilizes the polymer chains in the polymer without dissolving or melting it. This allows the organic material 110 to infiltrate the open spaces 108 as shown in FIG. 1C .
  • Suitable solvents include both organic and aqueoussolvents (e.g., water).
  • suitable organic solvents include but are not limited to acetone, chloroform, benzene, cyclohexane, dichloromethane, ethanol, diethyl ether, ethyl acetate, hexane, methanol, toluene, xylene, mixtures of two or more of these, and derivatives of one or more of these.
  • any solvent/organic material pair can be used.
  • the inventors have infiltrated anodized nanotemplates with P3HT and MEH—PPV using the solvent vapor treatment described above.
  • Infiltration of pores into anodized nanostructured templates (ANT) and titanium nanotubes (TNT) has been verified with scanning electron microscopy (SEM). Although there may be some gaps in the fill, the structure is reasonably close to fully filled.
  • some portion 114 of the organic material may remain disposed on the nanostructured material 102 after the spaces 108 have been infiltrated.
  • a photovoltaic device can then be fabricated from the resulting structure if the organic material 110 is a conductor or semiconductor and the nanostructured material 102 is a semiconductor having complementary charge transfer properties to the organic material 110 (i.e., if the organic material 110 is an electron transporter and the nanostructured material 102 is a hole transporter or vice versa).
  • a transparent electrode can then be disposed in electrical contact with the organic material 110 in the spaces 108 as shown in FIG. 1D .
  • the remaining portion 114 of the organic material can serve as a charge transporting.
  • Such a charge-transporting layer enhances electrical contact between the organic material 110 in the spaces 108 and the transparent electrode 114 .
  • the photovoltaic device can be encapsulated with an encapsulant layer 116 disposed on the transparent conducting layer 114 as shown in FIG. 1E .
  • Solvent vapor infiltration of organic material such as conjugated polymers into nanostructured templates has been demonstrated to be superior to thermal infiltration. Scanning electron micrographs show a greater degree of pore filling for solvent vapor infiltration compared to thermal infiltration. Furthermore, the device characteristics (e.g., current-voltage characteristics) of devices made using solvent vapor infiltration are generally superior to comparable devices made using thermal infiltration.
  • Solvent vapor infiltration of organic materials is not limited to nanostructured templates. Solvent vapor infiltration can be applied to filling spaces in nanostructures that have been formed by techniques such as surfactant temptation. Furthermore, solvent vapor infiltration can also be applied to filling organic materials into nanostructures in forms other than nanostructured templates. For example, as shown in FIG. 2A , groups of isolated such as nanotubes 202 could be blended within a polymer matrix having polymer chains 204 . After exposing the nanostructure-polymer mixture to solvent vapor, the polymer chains infiltrate the nanotubes as shown in FIG. 2B . The nanotubes 202 could be connected to each other by polymer chains leading to the possibility of self-assembly of the polymer chains 204 and nanotubes 202 into a well-ordered interdigitated array.
  • Embodiments of the present invention demonstrate that solvent vapor infiltration is a viable alternative to thermal infiltration.
  • Solvent vapor infiltration is particularly useful for MEH—PPV and other organic materials such as polymers that would otherwise require temperatures of order 200° C. or higher to melt/infiltrate material into spaces 5–1000 nm wide. In principle, however, solvent vapor infiltration can also be applied to spaces that are either narrower or wider than this range.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electromagnetism (AREA)
  • Mathematical Physics (AREA)
  • Theoretical Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Spaces in a nanostructure can be filled with an organic material while in the solid state below Tm (without heating) by exposing the organic material to solvent vapor while on or mixed with the nanostructured material. The exposure to solvent vapor results in intimate contact between the organic material and the nanostructured material without having to expose them to possibly detrimental heat to melt in the organic material. Solution processing methods need only to be employed to create bulk films while organic material infiltration can take place in the solid state after depositing the film.

Description

CROSS-REFERENCE TO RELATED APPLICATION
This application is related to commonly assigned, co-pending application Ser. No. 10/719,040, filed 21 Nov. 2003, the entire disclosures of which are incorporated herein by reference. This application is also related to commonly assigned U.S. patent application Ser. No. 10/443,456, the entire disclosures of which are incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates to processing of organic materials and more particularly to filling spaces in nanostructures with organic materials.
BACKGROUND OF THE INVENTION
Recently, devices have been developed that use electrically conducting and/or semiconductor polymers, or other organic materials, as active materials that fill empty spaces in nanometer-scale structures. Filling such spaces, e.g., pores, cavities, tubes, or interstitial spaces between pores, tubes or rods, with an organic material typically requires heating the polymer to temperatures up to 250° C. or more, depending on the type of organic material. Unfortunately, organic materials can be degraded by such heat treatment, which can be detrimental to the resulting device.
Thus, there is a need in the art, for a non-destructive method for depositing polymers into functional nanostructures without dissolving or melting the polymer.
BRIEF DESCRIPTION OF THE DRAWINGS
The teachings of the present invention can be readily understood by considering the following detailed description in conjunction with the accompanying drawings, in which:
FIGS. 1A–1C are a sequence of cross-sectional schematic diagrams illustrating a method for solvent vapor infiltration of a polymer into a nanostructure according to an embodiment of the present invention.
FIGS. 1D–1E are a sequence of cross-sectional schematic diagrams illustrating fabrication of a device.
FIGS. 2A–2B are a sequence of schematic diagrams illustrating solvent vapor infiltration of a polymer into nanotubes according to an alternative embodiment of the present invention.
 DESCRIPTION OF THE SPECIFIC EMBODIMENTS
Although the following detailed description contains many specific details for the purposes of illustration, anyone of ordinary skill in the art will appreciate that many variations and alterations to the following details are within the scope of the invention. Accordingly, the exemplary embodiments of the invention described below are set forth without any loss of generality to, and without imposing limitations upon, the claimed invention.
According to embodiments of the present invention, empty spaces in a nanostructure can be filled with a polymer or other organic material (such as a small molecule, e.g., fullerene, pigment, or dye) at room temperature by lowering the glass transition temperature Tg by exposing the polymer to solvent vapor while on or mixed with the nanostructured material. The exposure to solvent vapor results in intimate contact between the polymer and the nanostructured material without having to expose them to possibly detrimental heat to melt in the polymer. Solution processing methods need only to be employed to create bulk films while polymer infiltration can take place in the solid state after depositing the film.
For example, as shown in FIG. 1A, an organic material 110 is disposed on a nanostructured material 102. The nanostructured material may be formed or otherwise disposed on an electrode 104, e.g., a metal foil. The electrode 104 may be disposed on a substrate 106 such as a glass or polymer.
In preferred embodiments of the present invention the organic material 110 is a conducting or semiconducting polymer. Examples of such polymers include poly(phenylene) and derivatives thereof, poly(phenylene vinylene) and derivatives thereof (e.g., poly(2-methoxy-5-(2-ethyl-hexyloxy)-1,4-phenylene vinylene (MEH—PPV), poly(para-phenylene vinylene), (PPV)), PPV copolymers poly(thiophene) and derivatives thereof (e.g., poly(3-octylthiophene-2,5,-diyl), regioregular, poly(3-octylthiophene-2,5,-diyl), regiorandom, poly(3-hexylthiophene) (P3HT), poly(3-hexylthiophene-2,5-diyl), regioregular, poly(3-hexylthiophene-2,5-diyl), regiorandom), MDMO, poly(thienylenevinylene) and derivatives thereof, and poly(isothianaphthene) and derivatives thereof, tetra-hydro-thiophene precursors and derivatives thereof, poly-phenylene-vinylene and derivatives organometallic polymers, polymers containing perylene units, poly(squaraines) and their derivatives, discotic liquid crystals polyfluorenes, polyfluorene copolymers, polyfluorene-based copolymers and blends, e.g. co-polymerized and/or blended with charge transporting (e.g. tri-phenyl-amines and derivatives) and/or light-absorbing compounds (e.g. fused thiophene rings and derivatives, generally hetero-atom ring compounds with or without substituents), and/or fullerenes, dyes or pigments. In alternative embodiments the organic material 110 can be a fullerene, dye, pigment or other organic molecule such as pentacene or pentacene precursors.
The organic material 110 may be disposed on the nanostructured material 102 by any suitable technique, e.g., spin coating, web coating, doctor blade coating, spray coating, inkjet printing, organic vapor jet printing and the like.
The nanostructured material has numerous spaces 108 that are several nanometers across, e.g., between about 50 nm and about 1000 nm across. The nanostructures can be in the form of tubes in a nanotubular template, e.g., 1 nm to 1000 nm in diameter with a tube density between about 1012 tubes/m2 and about 1016 tubes/m2. Alternatively, the spaces 108 can be nanopores, cavities, or interstitial spaces between pores, tubes or rods. By way of example, the nanostructured material 102 may be fabricated by anodization techniques or surfactant temptation techniques. Examples of anodization techniques are described e.g., in commonly assigned co-pending U.S. patent application Ser. No. 10/443,456 filed May 21, 2003, which is incorporated herein by reference. Examples of surfactant temptation techniques are described in commonly assigned co-pending U.S. patent application Ser. Nos. 10/290,119 and 10/303,665 respectively filed Nov. 5, 2002 and Nov. 22, 2002, both of which are incorporated herein by reference.
As shown in FIG. 1B, the organic material 110 is exposed to a solvent vapor 112. For example, when the organic material 110 is a polymer, exposure to the solvent vapor 112 mobilizes the polymer chains in the polymer without dissolving or melting it. This allows the organic material 110 to infiltrate the open spaces 108 as shown in FIG. 1C. Suitable solvents include both organic and aqueoussolvents (e.g., water). Examples of suitable organic solvents include but are not limited to acetone, chloroform, benzene, cyclohexane, dichloromethane, ethanol, diethyl ether, ethyl acetate, hexane, methanol, toluene, xylene, mixtures of two or more of these, and derivatives of one or more of these.
Any solvent/organic material pair can be used. By way of example, the inventors have infiltrated anodized nanotemplates with P3HT and MEH—PPV using the solvent vapor treatment described above. Infiltration of pores into anodized nanostructured templates (ANT) and titanium nanotubes (TNT) has been verified with scanning electron microscopy (SEM). Although there may be some gaps in the fill, the structure is reasonably close to fully filled. Depending on the amount of organic material 110 initially disposed on the nanostructured material 102, some portion 114 of the organic material may remain disposed on the nanostructured material 102 after the spaces 108 have been infiltrated.
A photovoltaic device can then be fabricated from the resulting structure if the organic material 110 is a conductor or semiconductor and the nanostructured material 102 is a semiconductor having complementary charge transfer properties to the organic material 110 (i.e., if the organic material 110 is an electron transporter and the nanostructured material 102 is a hole transporter or vice versa). A transparent electrode can then be disposed in electrical contact with the organic material 110 in the spaces 108 as shown in FIG. 1D. For example, the remaining portion 114 of the organic material can serve as a charge transporting. Such a charge-transporting layer enhances electrical contact between the organic material 110 in the spaces 108 and the transparent electrode 114. The photovoltaic device can be encapsulated with an encapsulant layer 116 disposed on the transparent conducting layer 114 as shown in FIG. 1E.
Solvent vapor infiltration of organic material such as conjugated polymers into nanostructured templates has been demonstrated to be superior to thermal infiltration. Scanning electron micrographs show a greater degree of pore filling for solvent vapor infiltration compared to thermal infiltration. Furthermore, the device characteristics (e.g., current-voltage characteristics) of devices made using solvent vapor infiltration are generally superior to comparable devices made using thermal infiltration.
Solvent vapor infiltration of organic materials is not limited to nanostructured templates. Solvent vapor infiltration can be applied to filling spaces in nanostructures that have been formed by techniques such as surfactant temptation. Furthermore, solvent vapor infiltration can also be applied to filling organic materials into nanostructures in forms other than nanostructured templates. For example, as shown in FIG. 2A, groups of isolated such as nanotubes 202 could be blended within a polymer matrix having polymer chains 204. After exposing the nanostructure-polymer mixture to solvent vapor, the polymer chains infiltrate the nanotubes as shown in FIG. 2B. The nanotubes 202 could be connected to each other by polymer chains leading to the possibility of self-assembly of the polymer chains 204 and nanotubes 202 into a well-ordered interdigitated array.
Embodiments of the present invention demonstrate that solvent vapor infiltration is a viable alternative to thermal infiltration. Solvent vapor infiltration is particularly useful for MEH—PPV and other organic materials such as polymers that would otherwise require temperatures of order 200° C. or higher to melt/infiltrate material into spaces 5–1000 nm wide. In principle, however, solvent vapor infiltration can also be applied to spaces that are either narrower or wider than this range.
While the above is a complete description of the preferred embodiment of the present invention, it is possible to use various alternatives, modifications and equivalents. Therefore, the scope of the present invention should be determined not with reference to the above description but should, instead, be determined with reference to the appended claims, along with their full scope of equivalents. The appended claims are not to be interpreted as including means-plus-function limitations, unless such a limitation is explicitly recited in a given claim using the phrase “means for.”

Claims (20)

1. A method for infiltrating an organic material into spaces in one or more nanostructures, comprising:
disposing the organic material proximate the nanostructures; and
infiltrating the organic material into the spaces in the nanostructures by exposing the organic material to a solvent vapor.
2. The method of claim 1 wherein disposing the organic material proximate the nanostructures includes disposing a layer of a polymer process solution on a nanostructured template.
3. The method of claim 2 wherein the nanostructured template has spaces between about 5 nm and about 1000 nm wide.
4. The method of claim 2 wherein the spaces in the nanostructured template include tubes between about 1 nm and about 1000 nm in diameter with a tube density between about 1012 tubes/m2 and about 1016 tubes/m2.
5. The method of claim 1, wherein the nanostructures include one or more nanopores, cavities, or interstitial spaces between pores, tubes or rods.
6. The method of claim 5 wherein disposing the organic material proximate the nanostructures includes mixing the nanotubes into a polymer process solution.
7. The method of claim 1 wherein the organic material is a small molecule.
8. The method of claim 1 wherein the organic material is a pigment, dye or fullerene.
9. The method of claim 1 wherein the organic material is a polymer.
10. The method of claim 9 wherein the polymer includes one or more polymers selected from the group of poly(phenylene) and derivatives thereof, poly(phenylene vinylene) and derivatives thereof (e.g., poly(2-methoxy-5-(2-ethyl-hexyloxy)-1,4-phenylene vinylene (MEH—PPV), poly(para-phenylene vinylene), (PPV)), PPV copolymers, poly(thiophene) and derivatives thereof (e.g., regioregular poly(3-octylthiophene-2,5,-diyl), regiorandom poly(3-octylthiophene-2,5,-diyl), poly(3-hexylthiophene) (P3HT), regioregular poly(3-hexylthiophene-2,5-diyl), regiorandom poly(3-hexylthiophene-2,5-diyl)), MDMO, poly(thienylenevinylene) and derivatives thereof, and poly(isothianaphthene) and derivatives thereof, tetra-hydro-thiophene precursors and derivatives thereof, poly-phenylene-vinylene and derivatives organometallic polymers, polymers containing perylene units, poly(squaraines) and their derivatives, discotic liquid crystals polyfluorenes, polyfluorene copolymers, polyfluorene-based copolymers and blends, polyfluorene-based copolymers co-polymerized and/or blended with charge transporting compounds and/or light absorbing compounds, polyfluorene-based copolymers co-polymerized and/or blended with tri-phenyl-amines and derivatives, polyfluorene-based copolymers co-polymerized and/or blended with fused thiophene rings and derivatives, generally hetero-atom ring compounds with or without substituents, and/or fullerenes, dyes or pigments.
11. The method of claim 10 wherein the solvent vapor is selected from the group of acetone, chloroform, benzene, cyclohexane, dichloromethane, ethanol, diethyl ether, ethyl acetate, hexane, methanol, toluene, xylene, mixtures of two or more of these, and derivatives of one or more of these.
12. A method for making an optoelectronic device, comprising:
providing a nanostructured template having spaces between one or more nanostructures;
infiltrating an organic material into the spaces by disposing the organic material proximate the nanostructures and exposing the organic material to a solvent vapor; and
placing the nanostructured template and or organic material in electrical contact with an electrode.
13. The method of claim 12 wherein disposing the organic material proximate the nanostructures includes disposing a layer of an organic process solution on a nanostructured template.
14. The method of claim 12 wherein the spaces in the nanostructured template include tubes between about 1 nm and about 1000 nm in diameter with a tube density between about 1012 tubes/m2 and about 1016 tubes/m2.
15. The method of claim 12 wherein the organic material includes small molecules.
16. The method of claim 15 wherein the small molecules include pentacene or pentacene precursors.
17. The method of claim 12 wherein the organic material is a pigment, dye or fullerene.
18. The method of claim 12 wherein the organic material is a polymer.
19. The method of claim 18 wherein the polymer includes one or more polymers selected from the group of poly(phenylene) and derivatives thereof, poly(phenylene vinylene) and derivatives thereof (e.g., poly(2-methoxy-5-(2-ethyl-hexyloxy)-1,4-phenylene vinylene (MEH—PPV), poly(para-phenylene vinylene), (PPV)), PPV copolymers, poly(thiophene) and derivatives thereof regioregular poly(3-octylthiophene-2,5,-diyl), regiorandom poly(3-octylthiophene-2,5,-diyl), poly(3-hexylthiophene) (P3HT), regioregular poly(3-hexylthiophene-2,5-diyl), regiorandom poly(3-hexylthiophene-2,5-diyl), MDMO, poly(thienylenevinylene) and derivatives thereof, and poly(isothianaphthene) and derivatives thereof, tetra-hydro-thiophene precursors and derivatives thereof, poly-phenylene-vinylene and derivatives organometallic polymers, polymers containing perylene units, poly(squaraines) and their derivatives, discotic liquid crystals polyfluorenes, polyfluorene copolymers, polyfluorene-based copolymers and blends, polyfluorene-based copolymers co-polymerized and/or blended with charge transporting compounds and/or light absorbing compounds, polyfluorene-based copolymers co-polymerized and/or blended with tri-phenyl-amines and derivatives, polyfluorene-based copolymers co-polymerized and/or blended with fused thiophene rings and derivatives, generally hetero-atom ring compounds with or without substituents, and/or fullerenes, dyes or pigments.
20. The method of claim 12 wherein solvent vapor is selected from the group of acetone, chloroform, benzene, cyclohexane, dichloromethane, ethanol, diethyl ether, ethyl acetate, hexane, methanol, toluene, xylene, mixtures of two or more of these, and derivatives of one or more of these.
US10/719,041 2003-11-21 2003-11-21 Solvent vapor infiltration of organic materials into nanostructures Expired - Fee Related US6987071B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/719,041 US6987071B1 (en) 2003-11-21 2003-11-21 Solvent vapor infiltration of organic materials into nanostructures

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US10/719,041 US6987071B1 (en) 2003-11-21 2003-11-21 Solvent vapor infiltration of organic materials into nanostructures

Publications (1)

Publication Number Publication Date
US6987071B1 true US6987071B1 (en) 2006-01-17

Family

ID=35550749

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/719,041 Expired - Fee Related US6987071B1 (en) 2003-11-21 2003-11-21 Solvent vapor infiltration of organic materials into nanostructures

Country Status (1)

Country Link
US (1) US6987071B1 (en)

Cited By (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050098204A1 (en) * 2003-05-21 2005-05-12 Nanosolar, Inc. Photovoltaic devices fabricated from nanostructured template
US20050215067A1 (en) * 2004-03-26 2005-09-29 Kiyotaka Mori Combination insulator and organic semiconductor formed from self-assembling block co-polymers
US7227066B1 (en) * 2004-04-21 2007-06-05 Nanosolar, Inc. Polycrystalline optoelectronic devices based on templating technique
US20070160763A1 (en) * 2006-01-12 2007-07-12 Stanbery Billy J Methods of making controlled segregated phase domain structures
US20070157968A1 (en) * 2006-01-12 2007-07-12 Stanbery Billy J Compositions including controlled segregated phase domain structures
US20070160770A1 (en) * 2006-01-12 2007-07-12 Stanbery Billy J Apparatus for making controlled segregated phase domain structures
US20080176030A1 (en) * 2002-06-08 2008-07-24 Fonash Stephen J Lateral collection photovoltaics
US20080311028A1 (en) * 2007-06-18 2008-12-18 Stanbery Billy J Assemblies of anisotropic nanoparticles
US20090087622A1 (en) * 2005-12-01 2009-04-02 Ahmed Busnaina Directed Assembly of Carbon Nanotubes and Nanoparticles Using Nanotemplates With Nanotrenches
US20090266477A1 (en) * 2008-04-25 2009-10-29 Weisenberger Matthew C Lightweight thermal management material for enhancement of through-thickness thermal conductivity
US20100133093A1 (en) * 2009-04-13 2010-06-03 Mackie Neil M Method for alkali doping of thin film photovoltaic materials
US7772487B1 (en) 2004-10-16 2010-08-10 Nanosolar, Inc. Photovoltaic cell with enhanced energy transfer
US20100212733A1 (en) * 2009-02-20 2010-08-26 Miasole Protective layer for large-scale production of thin-film solar cells
US7785921B1 (en) 2009-04-13 2010-08-31 Miasole Barrier for doped molybdenum targets
CN101826580A (en) * 2010-04-23 2010-09-08 江门市低碳照明科技有限公司 Production process and application of novel LED substrate
US20100258180A1 (en) * 2009-02-04 2010-10-14 Yuepeng Deng Method of forming an indium-containing transparent conductive oxide film, metal targets used in the method and photovoltaic devices utilizing said films
US20100258191A1 (en) * 2009-04-13 2010-10-14 Miasole Method and apparatus for controllable sodium delivery for thin film photovoltaic materials
US20100310770A1 (en) * 2009-06-05 2010-12-09 Baosheng Sang Process for synthesizing a thin film or composition layer via non-contact pressure containment
US20110023955A1 (en) * 2007-06-26 2011-02-03 Fonash Stephen J Lateral collection photovoltaics
US20110024285A1 (en) * 2009-07-30 2011-02-03 Juliano Daniel R Method for alkali doping of thin film photovoltaic materials
US20110030800A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods for caigs silver-containing photovoltaics
US20110030582A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Polymeric precursors for caigas aluminum-containing photovoltaics
US20110030799A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods and materials for cis and cigs photovoltaics
US20110030755A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods for photovoltaic absorbers with controlled group 11 stoichiometry
US20110062049A1 (en) * 2009-09-11 2011-03-17 Pro-Pak Industries, Inc. Load tray and method for unitizing a palletized load
US20110067998A1 (en) * 2009-09-20 2011-03-24 Miasole Method of making an electrically conductive cadmium sulfide sputtering target for photovoltaic manufacturing
US7935558B1 (en) 2010-10-19 2011-05-03 Miasole Sodium salt containing CIG targets, methods of making and methods of use thereof
US20110117582A1 (en) * 2005-12-01 2011-05-19 Northeastern University Multi-biomarker biosensor
US20110146532A1 (en) * 2009-12-17 2011-06-23 Precursor Energetics, Inc. Molecular precursors for optoelectronics
US20110162696A1 (en) * 2010-01-05 2011-07-07 Miasole Photovoltaic materials with controllable zinc and sodium content and method of making thereof
US20110189080A1 (en) * 2010-02-04 2011-08-04 Curtis Calvin J Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom
US8048707B1 (en) 2010-10-19 2011-11-01 Miasole Sulfur salt containing CIG targets, methods of making and methods of use thereof
US8080280B1 (en) 2007-10-16 2011-12-20 Sandia Corporation Nanostructure templating using low temperature atomic layer deposition
US20120028406A1 (en) * 2007-04-25 2012-02-02 James Harris Hybrid photovoltaic cells and related methods
US8110738B2 (en) 2009-02-20 2012-02-07 Miasole Protective layer for large-scale production of thin-film solar cells
US8226839B1 (en) 2009-06-08 2012-07-24 Sandia Corporation Method of patterning an aerogel
US8418418B2 (en) 2009-04-29 2013-04-16 3Form, Inc. Architectural panels with organic photovoltaic interlayers and methods of forming the same
US8435825B2 (en) * 2007-01-11 2013-05-07 General Electric Company Methods for fabrication of nanowall solar cells and optoelectronic devices
CN103681286A (en) * 2012-08-30 2014-03-26 英飞凌科技股份有限公司 Method for manufacturing a layer arrangement, and a layer arrangement
US8709548B1 (en) 2009-10-20 2014-04-29 Hanergy Holding Group Ltd. Method of making a CIG target by spray forming
US8709335B1 (en) 2009-10-20 2014-04-29 Hanergy Holding Group Ltd. Method of making a CIG target by cold spraying
US8828782B2 (en) 2010-09-15 2014-09-09 Precursor Energetics, Inc. Annealing processes for photovoltaics
CN104737254A (en) * 2012-09-12 2015-06-24 韩国化学研究院 Solar cell having light-absorbing structure
US9105797B2 (en) 2012-05-31 2015-08-11 Alliance For Sustainable Energy, Llc Liquid precursor inks for deposition of In—Se, Ga—Se and In—Ga—Se
US9130084B2 (en) 2010-05-21 2015-09-08 Alliance for Substainable Energy, LLC Liquid precursor for deposition of copper selenide and method of preparing the same
US9142408B2 (en) 2010-08-16 2015-09-22 Alliance For Sustainable Energy, Llc Liquid precursor for deposition of indium selenide and method of preparing the same
US9169548B1 (en) 2010-10-19 2015-10-27 Apollo Precision Fujian Limited Photovoltaic cell with copper poor CIGS absorber layer and method of making thereof
US9447513B2 (en) 2010-10-21 2016-09-20 Hewlett-Packard Development Company, L.P. Nano-scale structures
US10043921B1 (en) 2011-12-21 2018-08-07 Beijing Apollo Ding Rong Solar Technology Co., Ltd. Photovoltaic cell with high efficiency cigs absorber layer with low minority carrier lifetime and method of making thereof
US10358535B2 (en) 2008-04-25 2019-07-23 The University Of Kentucky Research Foundation Thermal interface material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6630772B1 (en) * 1998-09-21 2003-10-07 Agere Systems Inc. Device comprising carbon nanotube field emitter structure and process for forming device
US20030203139A1 (en) * 1998-06-19 2003-10-30 Zhifeng Ren Free-standing and aligned carbon nanotubes and synthesis thereof
US20030206332A1 (en) * 2000-03-27 2003-11-06 Shunpei Yamazaki Self-light emitting device and method of manufacturing the same
US20040010048A1 (en) * 2002-07-06 2004-01-15 Evans Douglas G. Resorbable structure for treating and healing of tissue defects

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030203139A1 (en) * 1998-06-19 2003-10-30 Zhifeng Ren Free-standing and aligned carbon nanotubes and synthesis thereof
US6630772B1 (en) * 1998-09-21 2003-10-07 Agere Systems Inc. Device comprising carbon nanotube field emitter structure and process for forming device
US20030206332A1 (en) * 2000-03-27 2003-11-06 Shunpei Yamazaki Self-light emitting device and method of manufacturing the same
US20040010048A1 (en) * 2002-07-06 2004-01-15 Evans Douglas G. Resorbable structure for treating and healing of tissue defects

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"Glossary of Abbreviations and Plastics Terms" [online], [retrieved on Jun. 16, 2005]. Retrieved from the Internet <URL: from https://www.ctsmachinery.com.au/glossary.asp?letter=p&page=6>.
B. McCarthy, et al., "Microscopy studies of nanotube-conjugated polymer interactions," Synthetic Materials vol. 121, 2001, pp. 1225-1226. *
Emer Lahiff, et al., "Selective Positioning and Density Control of Nanotubes within a Polymer Thin Film," Nano Letters vol. 3, No. 10, 2003, pp. 1333-1337. *
Glenn Bartholomew and Alan J. Heeger in "Infiltration of Regioregular Poly[2,2'-(3hexylthiophene)] into Random Nanocrystalline TiO<SUB>2 </SUB>Networks", Adv. Funct. Mater., vol. 15, No. 4., Apr., 2005.
R. Haggenmueller, et al., "Aligned single-wall carbon nanotubes in composites by melt processing methods," Chemical Physics Letters vol. 330, 2000, pp. 219-225. *

Cited By (127)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080176030A1 (en) * 2002-06-08 2008-07-24 Fonash Stephen J Lateral collection photovoltaics
US8294025B2 (en) 2002-06-08 2012-10-23 Solarity, Llc Lateral collection photovoltaics
US20050098204A1 (en) * 2003-05-21 2005-05-12 Nanosolar, Inc. Photovoltaic devices fabricated from nanostructured template
US7605327B2 (en) 2003-05-21 2009-10-20 Nanosolar, Inc. Photovoltaic devices fabricated from nanostructured template
US8093489B2 (en) 2003-05-21 2012-01-10 Nanosolar, Inc. Photovoltaic devices fabricated from nanostructured template
US20050215067A1 (en) * 2004-03-26 2005-09-29 Kiyotaka Mori Combination insulator and organic semiconductor formed from self-assembling block co-polymers
US7176147B2 (en) * 2004-03-26 2007-02-13 Matsushita Electric Industrial Co., Ltd. Combination insulator and organic semiconductor formed from self-assembling block co-polymers
US7227066B1 (en) * 2004-04-21 2007-06-05 Nanosolar, Inc. Polycrystalline optoelectronic devices based on templating technique
US7772487B1 (en) 2004-10-16 2010-08-10 Nanosolar, Inc. Photovoltaic cell with enhanced energy transfer
US20110117582A1 (en) * 2005-12-01 2011-05-19 Northeastern University Multi-biomarker biosensor
US20090087622A1 (en) * 2005-12-01 2009-04-02 Ahmed Busnaina Directed Assembly of Carbon Nanotubes and Nanoparticles Using Nanotemplates With Nanotrenches
US8668978B2 (en) 2005-12-01 2014-03-11 Northeastern University Multi-biomarker biosensor
US9388047B2 (en) * 2005-12-01 2016-07-12 Northeastern University Directed assembly of carbon nanotubes and nanoparticles using nanotemplates
US20070157968A1 (en) * 2006-01-12 2007-07-12 Stanbery Billy J Compositions including controlled segregated phase domain structures
US7767904B2 (en) 2006-01-12 2010-08-03 Heliovolt Corporation Compositions including controlled segregated phase domain structures
US8647533B2 (en) 2006-01-12 2014-02-11 Heliovolt Corporation Compositions including controlled segregated phase domain structure with segregated phase domain array
US20070160770A1 (en) * 2006-01-12 2007-07-12 Stanbery Billy J Apparatus for making controlled segregated phase domain structures
US8084685B2 (en) 2006-01-12 2011-12-27 Heliovolt Corporation Apparatus for making controlled segregated phase domain structures
US20070160763A1 (en) * 2006-01-12 2007-07-12 Stanbery Billy J Methods of making controlled segregated phase domain structures
US8435825B2 (en) * 2007-01-11 2013-05-07 General Electric Company Methods for fabrication of nanowall solar cells and optoelectronic devices
US8394663B2 (en) * 2007-04-25 2013-03-12 Nanoco Technologies, Ltd. Hybrid photovoltaic cells and related methods
US20120028406A1 (en) * 2007-04-25 2012-02-02 James Harris Hybrid photovoltaic cells and related methods
US8034317B2 (en) 2007-06-18 2011-10-11 Heliovolt Corporation Assemblies of anisotropic nanoparticles
US7939048B2 (en) 2007-06-18 2011-05-10 Heliovolt Corporation Assemblies of anisotropic nanoparticles
US20080311028A1 (en) * 2007-06-18 2008-12-18 Stanbery Billy J Assemblies of anisotropic nanoparticles
US20110023955A1 (en) * 2007-06-26 2011-02-03 Fonash Stephen J Lateral collection photovoltaics
US8080280B1 (en) 2007-10-16 2011-12-20 Sandia Corporation Nanostructure templating using low temperature atomic layer deposition
US10358535B2 (en) 2008-04-25 2019-07-23 The University Of Kentucky Research Foundation Thermal interface material
US8632879B2 (en) 2008-04-25 2014-01-21 The University Of Kentucky Research Foundation Lightweight thermal management material for enhancement of through-thickness thermal conductivity
US20090266477A1 (en) * 2008-04-25 2009-10-29 Weisenberger Matthew C Lightweight thermal management material for enhancement of through-thickness thermal conductivity
US20100258180A1 (en) * 2009-02-04 2010-10-14 Yuepeng Deng Method of forming an indium-containing transparent conductive oxide film, metal targets used in the method and photovoltaic devices utilizing said films
US8110738B2 (en) 2009-02-20 2012-02-07 Miasole Protective layer for large-scale production of thin-film solar cells
US8115095B2 (en) 2009-02-20 2012-02-14 Miasole Protective layer for large-scale production of thin-film solar cells
US8389321B2 (en) 2009-02-20 2013-03-05 Miasole Protective layer for large-scale production of thin-film solar cells
US20100212733A1 (en) * 2009-02-20 2010-08-26 Miasole Protective layer for large-scale production of thin-film solar cells
US8134069B2 (en) 2009-04-13 2012-03-13 Miasole Method and apparatus for controllable sodium delivery for thin film photovoltaic materials
US7785921B1 (en) 2009-04-13 2010-08-31 Miasole Barrier for doped molybdenum targets
US20100133093A1 (en) * 2009-04-13 2010-06-03 Mackie Neil M Method for alkali doping of thin film photovoltaic materials
US20110171395A1 (en) * 2009-04-13 2011-07-14 Miasole Method of forming a sputtering target
US7927912B2 (en) 2009-04-13 2011-04-19 Miasole Method of forming a sputtering target
US8017976B2 (en) 2009-04-13 2011-09-13 Miasole Barrier for doped molybdenum targets
US8313976B2 (en) 2009-04-13 2012-11-20 Mackie Neil M Method and apparatus for controllable sodium delivery for thin film photovoltaic materials
US20100310783A1 (en) * 2009-04-13 2010-12-09 Miasole Barrier for doped molybdenum targets
US7897020B2 (en) 2009-04-13 2011-03-01 Miasole Method for alkali doping of thin film photovoltaic materials
US20100307915A1 (en) * 2009-04-13 2010-12-09 Miasole Barrier for doped molybdenum targets
US20100258191A1 (en) * 2009-04-13 2010-10-14 Miasole Method and apparatus for controllable sodium delivery for thin film photovoltaic materials
US8076174B2 (en) 2009-04-13 2011-12-13 Miasole Method of forming a sputtering target
US9076731B2 (en) 2009-04-29 2015-07-07 3Form, Llc Architectural panels with organic photovoltaic interlayers and methods of forming the same
US8418418B2 (en) 2009-04-29 2013-04-16 3Form, Inc. Architectural panels with organic photovoltaic interlayers and methods of forming the same
US20100310770A1 (en) * 2009-06-05 2010-12-09 Baosheng Sang Process for synthesizing a thin film or composition layer via non-contact pressure containment
US8226839B1 (en) 2009-06-08 2012-07-24 Sandia Corporation Method of patterning an aerogel
US20110024285A1 (en) * 2009-07-30 2011-02-03 Juliano Daniel R Method for alkali doping of thin film photovoltaic materials
US9284639B2 (en) 2009-07-30 2016-03-15 Apollo Precision Kunming Yuanhong Limited Method for alkali doping of thin film photovoltaic materials
US20110030755A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods for photovoltaic absorbers with controlled group 11 stoichiometry
US8512603B2 (en) 2009-08-04 2013-08-20 Precursor Energetics, Inc. Polymeric precursors for CIS and CIGS photovoltaics
US20110030800A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods for caigs silver-containing photovoltaics
US20110030582A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Polymeric precursors for caigas aluminum-containing photovoltaics
US20110030796A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods and articles for caigs silver-containing photovoltaics
US8741182B2 (en) 2009-08-04 2014-06-03 Precursor Energetics, Inc. Methods and materials for AIGS silver-containing photovoltaics
US8721930B2 (en) 2009-08-04 2014-05-13 Precursor Energetics, Inc. Polymeric precursors for AIGS silver-containing photovoltaics
US8715775B2 (en) 2009-08-04 2014-05-06 Precursor Energetics, Inc. Precursors and uses for CIS and CIGS photovoltaics
US20110030799A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods and materials for cis and cigs photovoltaics
US20110034667A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Processes for polymeric precursors for aigs silver-containing photovoltaics
US20110030784A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods and materials for caigs silver-containing photovoltaics
US8617431B2 (en) 2009-08-04 2013-12-31 Precursor Energetics, Inc. Selenolate inks and precursors for photovoltaics
US8067626B2 (en) 2009-08-04 2011-11-29 Precursor Energetics, Inc. Processes for polymeric precursors for CAIGS silver-containing photovoltaics
US8067262B2 (en) 2009-08-04 2011-11-29 Precursor Energetics, Inc. Polymeric precursors for CAIGS silver-containing photovoltaics
US20110041918A1 (en) * 2009-08-04 2011-02-24 Precursor Energetics, Inc. Methods and materials for aigs silver-containing photovoltaics
US20110030785A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods and materials for caigas aluminum-containing photovoltaics
US20110030786A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods for cis and cigs photovoltaics
US20110030581A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Polymeric precursors for aigs silver-containing photovoltaics
US20110034640A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Processes for polymeric precursors for cis and cigs photovoltaics
US20110030798A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods and articles for caigas aluminum-containing photovoltaics
US20110031445A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Processes for polymeric precursors for caigs silver-containing photovoltaics
US20110030797A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods and articles for aigs silver-containing photovoltaics
US8158033B2 (en) 2009-08-04 2012-04-17 Precursor Energetics, Inc. Polymeric precursors for CAIGAS aluminum-containing photovoltaics
US8168090B2 (en) 2009-08-04 2012-05-01 Precursor Energetics, Inc. Processes for polymeric precursors for CIS and CIGS photovoltaics
US20110034605A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Polymeric precursors for caigs silver-containing photovoltaics
US20110030787A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods for aigs silver-containing photovoltaics
US20110031453A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Processes for polymeric precursors for caigas aluminum-containing photovoltaics
US8318050B2 (en) 2009-08-04 2012-11-27 Precursor Energetics, Inc. Processes for polymeric precursors for caigas aluminum-containing photovoltaics
US8591775B2 (en) 2009-08-04 2013-11-26 Precursor Energetics, Inc. Methods and articles for CIS and CIGS photovoltaics
US20110030788A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods for caigas aluminum-containing photovoltaics
US20110030768A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods for photovoltaic absorbers with controlled group 13 stoichiometry
US20110031444A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Polymeric precursors for cis and cigs photovoltaics
US20110030795A1 (en) * 2009-08-04 2011-02-10 Precursor Energetics, Inc. Methods and articles for cis and cigs photovoltaics
US8440114B2 (en) 2009-08-04 2013-05-14 Precursor Energetics, Inc. Methods and materials for CAIGAS aluminum-containing photovoltaics
US8449793B2 (en) 2009-08-04 2013-05-28 Precursor Energetics, Inc. Methods and articles for CAIGAS aluminum-containing photovoltaics
US8465679B2 (en) 2009-08-04 2013-06-18 Precursor Energetics, Inc. Methods for CAIGAS aluminum-containing photovoltaics
US8497390B2 (en) 2009-08-04 2013-07-30 Precursor Energetics, Inc. Methods and articles for CAIGS silver-containing photovoltaics
US8585936B2 (en) 2009-08-04 2013-11-19 Precursor Energetics, Inc. Methods for photovoltaic absorbers with controlled group 11 stoichiometry
US8545734B2 (en) 2009-08-04 2013-10-01 Precursor Energetics, Inc. Methods for photovoltaic absorbers with controlled group 13 stoichiometry
US8585932B2 (en) 2009-08-04 2013-11-19 Precursor Energetics, Inc. Methods and articles for AIGS silver-containing photovoltaics
US8585933B2 (en) 2009-08-04 2013-11-19 Precursor Energetics, Inc. Methods for AIGS silver-containing photovoltaics
US20110062049A1 (en) * 2009-09-11 2011-03-17 Pro-Pak Industries, Inc. Load tray and method for unitizing a palletized load
US20110067998A1 (en) * 2009-09-20 2011-03-24 Miasole Method of making an electrically conductive cadmium sulfide sputtering target for photovoltaic manufacturing
US9352342B2 (en) 2009-10-20 2016-05-31 Beijing Apollo Ding Rong Solar Technology Co., Ltd. Method of making a CIG target by cold spraying
US8709335B1 (en) 2009-10-20 2014-04-29 Hanergy Holding Group Ltd. Method of making a CIG target by cold spraying
US8709548B1 (en) 2009-10-20 2014-04-29 Hanergy Holding Group Ltd. Method of making a CIG target by spray forming
US20110146764A1 (en) * 2009-12-17 2011-06-23 Precursor Energetics, Inc. Molecular precursor methods and articles for optoelectronics
US20110146532A1 (en) * 2009-12-17 2011-06-23 Precursor Energetics, Inc. Molecular precursors for optoelectronics
US20110146790A1 (en) * 2009-12-17 2011-06-23 Precursor Energetics, Inc. Molecular precursor methods for optoelectronics
US8628696B2 (en) 2009-12-17 2014-01-14 Precursor Energetics, Inc. Molecular precursors for optoelectronics
US20110146789A1 (en) * 2009-12-17 2011-06-23 Precursor Energetics, Inc. Molecular precursor methods and materials for optoelectronics
US8715537B2 (en) 2009-12-17 2014-05-06 Precursor Energetics, Inc. Molecular precursor methods and materials for optoelectronics
US20110162696A1 (en) * 2010-01-05 2011-07-07 Miasole Photovoltaic materials with controllable zinc and sodium content and method of making thereof
US8021641B2 (en) 2010-02-04 2011-09-20 Alliance For Sustainable Energy, Llc Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom
US20110189080A1 (en) * 2010-02-04 2011-08-04 Curtis Calvin J Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom
CN101826580A (en) * 2010-04-23 2010-09-08 江门市低碳照明科技有限公司 Production process and application of novel LED substrate
US9130084B2 (en) 2010-05-21 2015-09-08 Alliance for Substainable Energy, LLC Liquid precursor for deposition of copper selenide and method of preparing the same
US9142408B2 (en) 2010-08-16 2015-09-22 Alliance For Sustainable Energy, Llc Liquid precursor for deposition of indium selenide and method of preparing the same
US8883550B2 (en) 2010-09-15 2014-11-11 Precursor Energetics, Inc. Deposition processes for photovoltaic devices
US8828782B2 (en) 2010-09-15 2014-09-09 Precursor Energetics, Inc. Annealing processes for photovoltaics
US8828787B2 (en) 2010-09-15 2014-09-09 Precursor Energetics, Inc. Inks with alkali metals for thin film solar cell processes
US8338214B2 (en) 2010-10-19 2012-12-25 Miasole Sodium salt containing CIG targets, methods of making and methods of use thereof
US7935558B1 (en) 2010-10-19 2011-05-03 Miasole Sodium salt containing CIG targets, methods of making and methods of use thereof
US9169548B1 (en) 2010-10-19 2015-10-27 Apollo Precision Fujian Limited Photovoltaic cell with copper poor CIGS absorber layer and method of making thereof
US8048707B1 (en) 2010-10-19 2011-11-01 Miasole Sulfur salt containing CIG targets, methods of making and methods of use thereof
US9447513B2 (en) 2010-10-21 2016-09-20 Hewlett-Packard Development Company, L.P. Nano-scale structures
US10043921B1 (en) 2011-12-21 2018-08-07 Beijing Apollo Ding Rong Solar Technology Co., Ltd. Photovoltaic cell with high efficiency cigs absorber layer with low minority carrier lifetime and method of making thereof
US10211351B2 (en) 2011-12-21 2019-02-19 Beijing Apollo Ding Rong Solar Technology Co., Ltd. Photovoltaic cell with high efficiency CIGS absorber layer with low minority carrier lifetime and method of making thereof
US9105797B2 (en) 2012-05-31 2015-08-11 Alliance For Sustainable Energy, Llc Liquid precursor inks for deposition of In—Se, Ga—Se and In—Ga—Se
CN103681286A (en) * 2012-08-30 2014-03-26 英飞凌科技股份有限公司 Method for manufacturing a layer arrangement, and a layer arrangement
CN103681286B (en) * 2012-08-30 2018-01-16 英飞凌科技股份有限公司 The manufacture method of layer arrangement and layer arrangement
JP2015529982A (en) * 2012-09-12 2015-10-08 コリア リサーチ インスティテュート オブ ケミカル テクノロジー Solar cell with light absorbing structure
CN104737254A (en) * 2012-09-12 2015-06-24 韩国化学研究院 Solar cell having light-absorbing structure
US10546697B2 (en) 2012-09-12 2020-01-28 Korea Research Institute Of Chemical Technology Solar cell having light-absorbing structure

Similar Documents

Publication Publication Date Title
US6987071B1 (en) Solvent vapor infiltration of organic materials into nanostructures
Chen et al. Conjugated polymer nanostructures for organic solar cell applications
Kang et al. Effective Use of Electrically Insulating Units in Organic Semiconductor Thin Films for High‐Performance Organic Transistors
Ahmad Organic semiconductors for device applications: current trends and future prospects
EP2210291B1 (en) Processing additives for fabricating organic photovoltaic cells
Salim et al. The role of poly (3-hexylthiophene) nanofibers in an all-polymer blend with a polyfluorene copolymer for solar cell applications
KR101312269B1 (en) Polymer solar cell and preparation method thereof
KR101461634B1 (en) High―efficiency Inorganic―Organic Hybrid Solar Cells and Their Fabrication Methods
US20090126796A1 (en) Highly Efficient Polymer Solar Cell by Polymer Self-Organization
Xie et al. Fluorene-based macromolecular nanostructures and nanomaterials for organic (opto) electronics
JP2009514202A (en) Polymer nanofiber network for photovoltaic cells
EP3451399A1 (en) Organic electronic element and method for manufacturing same
KR20070034492A (en) Electronic devices
WO2014042447A2 (en) Method for manufacturing solar cell having light-absorbing structure
Rammal et al. Recent advances in the green processing of organic photovoltaic devices from nanoparticle dispersions
US20110237020A1 (en) Methods for controlling the crystalline nanofibre content of organic layers used in organic electronic devices
JP2006270061A (en) Photovoltaic device
Yu et al. Fabrication of one-dimensional organic nanomaterials and their optoelectronic applications
US20130014818A1 (en) Conductive Polymer/Fullerence Blend Thin Films with Honeycomb Framework for Transparent Photovoltaic Application
JP5362017B2 (en) Organic thin film solar cell
JP2010192863A (en) Organic photoelectric conversion element and method of manufacturing the same
US7829143B1 (en) Solvent vapor annealing of organic films
Zheng et al. Construction of laterally asymmetric heterojunctions with sub‐micrometer resolution by hierarchical self‐assembly of polythiophene nanofibers
US20070158646A1 (en) Organic semiconductor having polymeric and nonpolymeric constituents
KR100926263B1 (en) Conducting polymer composite film photovoltaic device prepared by electrochemical polymerization using conducting monomer functional group modified fullerene derivative and method for fabricating the same

Legal Events

Date Code Title Description
AS Assignment

Owner name: NANOSOLAR INC., CALIFORNIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BOLLMAN, BRENT J.;PETRITSCH, KLAUS;ROBINSON, MATTHEW R.;REEL/FRAME:014742/0720

Effective date: 20031118

REMI Maintenance fee reminder mailed
FPAY Fee payment

Year of fee payment: 4

SULP Surcharge for late payment
AS Assignment

Owner name: AERIS CAPITAL SUSTAINABLE IMPACT PRIVATE INVESTMEN

Free format text: SECURITY AGREE,EMT;ASSIGNOR:NANOSOLAR, INC.;REEL/FRAME:029556/0418

Effective date: 20121109

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

REMI Maintenance fee reminder mailed
FPAY Fee payment

Year of fee payment: 8

SULP Surcharge for late payment

Year of fee payment: 7

AS Assignment

Owner name: AERIS CAPITAL SUSTAINABLE IP LTD., CAYMAN ISLANDS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:NANOSOLAR, INC.;REEL/FRAME:033145/0686

Effective date: 20131223

FEPP Fee payment procedure

Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.)

LAPS Lapse for failure to pay maintenance fees

Free format text: PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.)

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20180117